CN101503770A - Cu-Ni-Si-based copper alloy sheet material and method of manufacturing same - Google Patents
Cu-Ni-Si-based copper alloy sheet material and method of manufacturing same Download PDFInfo
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Abstract
This invention provides a copper alloy sheet material containing, in mass%, Ni: 0.7% - 4.2% and Si: 0.2% - 1.0%, optionally containing one or more of Sn: 1.2% or less, Zn: 2.0% or less, Mg: 1.0% or less, and Co: 2.0% or less, and a total of 3% or less of one or more of Cr, B, P, Zr, Ti, Mn and V, the balance being substantially Cu, and having a crystal orientation satisfying Expression (1): where I{420} is the x-ray diffraction intensity from the {420} crystal plane in the sheet plane of the copper alloy sheet material and I 0 {420} is the x-ray diffraction intensity from the {420} crystal plane of standard pure copper powder. The copper alloy sheet material has highly improved strength, post-notching bending workability, and stress relaxation resistance property.
Description
Technical field
The present invention relates to as unitor frame material (lead frame), rly., electrical and electronic parts such as the switch Cu-Ni-Si series copper alloy sheet material and the manufacture method thereof of material.This copper alloy has good electrical conductivity and high-intensity while, particularly has excellent bendability and proof stress slackness.
Background technology
Unitor, frame material, rly., electrical and electronic parts such as switch with material in use, the heat that produces in order to suppress to switch on requires material to have good electrical conductivity.Simultaneously, when working and assemble viscous deformation not taking place in order to guarantee electrical and electronic parts, requires material to have sufficiently high intensity.And electrical and electronic parts generally is shaped by crooked, therefore requires material to have excellent in vending workability.In addition, in order to guarantee the reliability of the contact between electrical and electronic parts, (so-called stress relaxation is the phenomenon that the contact pressure between electrical and electronic parts reduces in time to require material to have good proof stress slackness.)
Particularly in recent years, along with the densification of electrical and electronic parts, miniaturization and lightweight require employed copper base alloy more and more thinner, thereby require material to have higher intensity.Specifically, the tensile strength that requires material is preferably in more than the 750MPa more than 700MPa.
And along with electrical and electronic parts becomes more and more littler, its shape becomes and becomes increasingly complex, and is also more and more higher to the requirement of the shape and size precision after the material bending machining.Therefore, indent bending machining method is adopted in actual production more and more in recent years.So-called " indent bending machining method " is exactly to want crooked position to press a groove earlier, and then carries out bending machining.Can greatly improve the shape and size precision after the bending machining like this.But, because near the work hardening capacity the indent time slot is very big, rupture easily during bending machining after the indent.Therefore, this processing method requires very strict to the bendability of material.
In addition, along with electrical and electronic parts uses the increase of chance under rugged environment, also more and more higher to the requirement of the proof stress slackness of material.For example, resemble automobile when with unitor, under than higher temperature, using, the proof stress slackness particularly important that just seems.So-called stress relaxation is meant, keeps at normal temperatures necessarily though constitute the contact pressure at electrical and electronic parts spring position, under than higher temperature (for example 100～200 ℃), in time and the creep of minimizing.That is to say that metallic substance makes added stress by lax because the dislocation moving that the diffusion of the self-diffusion of matrix atom and solid solution atom causes has produced viscous deformation.
, between electroconductibility and the intensity, all exist the relation of opposite each other (that disappears this length) between intensity and the bendability and between bendability and the proof stress slackness.It is very very difficult will improving these characteristics simultaneously, therefore, when electrical and electronic parts is made, often according to purposes, comes select materials by above-mentioned each characteristic is weighed now.
Cu-Ni-Si is alloy (a so-called Corson alloy) and since it electroconductibility (electric conductivity: 30～45% IACS) and intensity balance relatively good, gazed in recent years., as everyone knows, improve the intensity and the bendability of Cu-Ni-Si series copper alloy simultaneously, perhaps bendability and proof stress slackness but are very difficult.
Raising Cu-Ni-Si is that the method for alloy strength generally has two, promptly increases the amount of solute elements such as Ni and Si, and increases the rolling rate after the ageing treatment., the former since excessive N i-Si shape precipitate cause the decline of electroconductibility and cause the decline of bendability; The latter is because excessive work hardening causes the decline of bendability (particularly perpendicular to the bendability of rolling direction, that is, for the bendability of the bending axis that is parallel to rolling direction).Therefore, even very high intensity and electroconductibility are arranged, also can be owing to can not bending forming and can not use with material as electrical and electronic parts.
For fear of the reduction of bendability, common means are cold rolling (or the reducing rolling rate as much as possible) after the omission ageing treatment, remedy the deficiency of intensity by the amount that improves solute elements such as Ni and Si., this method has increased materials processing hardened trend, and when utilizing indent bending machining method in this state, near the work hardening capacity groove is very big, therefore produces the problem of the serious deterioration of bendability when the indent bending machining.
In addition, crystal grain thinning also is the conventional means that improves bendability.But, when Cu-Ni-Si is the solution treatment of alloy, do not carry out solution treatment and make all precipitates (or crystallized product) enter sosoloid, thereby but keep a part of precipitate (or crystallized product) at relative low-temperature region and stop growing up of crystal grain at high-temperature area.Therefore, owing to be in the minimizing of the Ni and the Si of solid solution condition after the solution treatment, the intensity after the ageing treatment also just must decrease.
And grain-size is more little, and the grain boundary area in the unit volume is just big more.Because the velocity of diffusion of atoms along grain boundary is much larger than the velocity of diffusion of atom in crystal grain inside, therefore, the too tiny reduction that causes easily as a kind of proof stress slackness of creep of crystal grain.Resemble automobile especially when using under than higher temperature with unitor, the reduction of proof stress slackness might lead to disastrous consequence.
In recent years, the method for utilizing the crystalline orientation (texture) of controlling sheet material to improve the bendability of Cu-Ni-Si series copper alloy is gazed at.At following patent documentation 1～5 more specific record is arranged.
The open 2000-80428 communique of [patent documentation 1] Japanese Patent
The open 2006-9108 communique of [patent documentation 2] Japanese Patent
The open 2006-16629 communique of [patent documentation 3] Japanese Patent
The open 2006-9137 communique of [patent documentation 4] Japanese Patent
The open 2006-152392 communique of [patent documentation 5] Japanese Patent
Now, there are two kinds of methods to be considered to be used to improve the bendability of copper alloy, promptly control sheet material texture and crystal grain thinning.To the evaluation of metal plate-like material texture, the most frequently used method is the X-ray diffraction intensity with each crystal plane in X-ray diffraction device (XRD) the assay plate surface (rolling surface).The Cu-Ni-Si series copper alloy is under common creating conditions, mainly contain in the X ray diffracting spectrum that { 111}, { 200}, { 220}, { there is the diffracted intensity peak in four crystal planes of 311}, in other words, the X-ray diffraction intensity of other crystal plane is compared very little so that can ignore with these crystal planes.After the solution treatment (recrystallize), { 200} is with { X-ray diffraction intensity of 311} crystal plane is very high.Cold rolling along with after this, the X-ray diffraction intensity of these crystal planes reduces, and { X-ray diffraction intensity of 220} crystal plane strengthens relatively.{ variation of the X-ray diffraction intensity of 111} crystal plane is very little owing to cold rolling.
In patent documentation 1,, stipulated that { 200}, { 220}, { X-ray diffraction intensity of three crystal planes of 311} must satisfy following relational expression in order to improve the bendability of Cu-Ni-Si series copper alloy.That is,
(I{200}+I{311})/I{220}>0.5
This relational expression comes down to expression, improves bendability by the cold rolling rate after the reduction solution treatment.Tend to follow the reduction of intensity like this.Such as, the tensile strength that obtains in patent documentation 1 is between 560～670MPa.
At patent documentation 4 method that relational expression below satisfying is improved bendability is proposed.That is: I{311} * A/ (I{311}+I{220}+I{200})＜1.5.Wherein, A is a crystal grain diameter.
Proposed at patent documentation 5, and 001}＜100〉percentage of (so-called Cube) texture is more than 50%, average crystal grain diameter is below the 10 μ m simultaneously.These methods all require the grain-size refinement simultaneously, often cause the reduction of proof stress slackness easily.
And, even adopt the method that resembles in the patent documentation 1～5 to improve the common bendability of Cu-Ni-Si series copper alloy, also be difficult to improve above-mentioned indent bending machining method.Although adopt the shape and size precision after indent bending machining method can greatly improve bending machining, do not consider the problem that crackle takes place when preventing the indent bending machining in the patent documentation 1～5.
In addition, as mentioned above,, unfavorable to proof stress slackness as a kind of creep though the crystal grain thinning method is favourable to improving bendability.Even so only considering to improve bendability all very under the situation of difficult, improve the proof stress slackness more simultaneously, it is irrealizable utilizing present known technology.
In view of above-mentioned present situation, the present invention is a purpose so that the Cu-Ni-Si series copper alloy with following feature to be provided.Promptly keeping under the high-intensity prerequisite, having and to satisfy the excellent in vending workability that indent bending machining method requires, having simultaneously and for example can satisfy automobile with the proof stress slackness of the environment for use of the such harshness of unitor.
Summary of the invention
Present inventors discover based on detailed investigation, if represent rolled plate normal to a surface direction with ND, LD represents rolling direction, and during TD is illustrated in the plate face and ND and LD are perpendicular direction, all the grain orientation of easy deformation exists on these three directions.And be that main texture can and be created conditions by the control alloying constituent and be obtained by special like this grain orientation.The present invention is based on these discoveries and finishes.
The invention provides a kind of copper alloy plate, it contains the Ni of 0.7～4.2 weight % and the Si of 0.2～1.0 weight %, contain the following Sn of 1.2 weight % alternatively, 2.0 the Zn that weight % is following, 1.0 the Mg that weight % is following, 2.0 one or more among the following Fe of Co that weight % is following and 1.0 weight %, and also contain total amount and be 3 weight % following be selected from Cr, B, P, Zr, Ti, one or more among Mn and the V, all the other are essentially Cu, this copper alloy plate has satisfied following formula (1), and the grain orientation of formula (2) concerns below preferably also satisfying
I{420}/I
0{420}>1.0......(1)
I{220}/I
0{220}≦3.0......(2)
Wherein I{420} is this copper alloy plate surface { X-ray diffraction intensity of 420} crystal plane; I
0{ 420} is the standard pure copper powder { X-ray diffraction intensity of 420} crystal plane.I{420} and I
0{ condition determination of 420} is identical.Equally, I{220} is this copper alloy plate surface { X-ray diffraction intensity of 220} crystal plane; I
0{ 220} is the standard pure copper powder { X-ray diffraction intensity of 220} crystal plane.I{220} and I
0{ condition determination of 220} is also identical." all the other are essentially Cu " is meant, in the scope that does not influence effect of the present invention, allows above-mentioned element element in addition to sneak into.Therefore, all the other are Cu and comprise unavoidable impurities.
The average crystal grain diameter of above-mentioned copper alloy plate is particularly preferred between 10～60 μ m.Average crystal grain diameter can be examined under a microscope after the surface of sample (rolling surface) is through polishing and corrosion, and the division lines method of pressing among the JIS H0501 is measured.
The manufacture method of this copper alloy plate is provided, this method comprises that the copper alloy to having above-mentioned composition carries out following steps in turn, hot rolling between 950～400 ℃, rolling rate (reductionratio) is cold rolling more than 85%, solution treatment between 700～850 ℃, rolling rate is cold rolling in 0～50% centre, ageing treatment between 400～500 ℃, with rolling rate 0～50% finally cold rolling, in course of hot rolling, in 950 ℃～700 ℃ temperature provinces, carry out initial rolling pass, and preferred rolling rate in 950 ℃～700 ℃ temperature provinces is more than 60%, the rate that is rolled in being lower than 700 ℃～400 ℃ temperature provinces rolling more than 40%.
Here, the rolling rate ε of each temperature range is calculated by formula (3).
ε(％)＝(t
0-t
1)/t
0×100......(3)
Wherein, t
0(mm) be thickness of slab before first rolling pass in this temperature range continuous rolling passage of carrying out; t
1(mm) be thickness of slab after final rolling pass is finished in a plurality of rolling passes.
Wherein, " hot rollings between 950～400 ℃ " are meant that rolling pass is carried out between 950～400 ℃.Above-mentioned centre cold rolling and final cold rolling in, rolling rate is to represent not carry out the cold rolling of this stage at 0% o'clock.That is to say, one of cold rolling and final cold rolling both in the middle of can omitting, or both omit simultaneously.
In above-mentioned solution treatment, from heating-up time of 100 ℃ to 700 ℃ temperature ranges preferably below 20 seconds, and preferably carry out solution treatment by setting soaking time and outlet temperature 700～850 ℃ temperature range, the average crystal grain diameter after the solution treatment is between 10～60 μ m.If carried out final cold rolling, in final low-temperature annealing of preferably carrying out 150～550 ℃ after cold rolling.
Can obtain having the high strength more than the 700MPa according to the present invention, have and to satisfy the excellent in vending workability that indent bending machining method requires, can satisfy such as the unitor of automobile with the proof stress slackness of the excellence of the environment for use of harshnesses such as unitor, frame material, rly., electrical and electronic parts materials such as switch.By present manufacturing techniques available is the Cu-Ni-Si series copper alloy that is difficult to obtain to have above excellent specific property.Therefore, the present invention predictablely produces the miniaturization and the densification needs of electrical and electronic parts from now in order to satisfy.
Description of drawings
Fig. 1: the distribution of the Heidi Schmid factor of face-centered cubic crystal on the contrary pole graph of standard.
Fig. 2: the contrary pole graph of using the example No.1 of EBSP method mensuration.
Fig. 3: the contrary pole graph of using the comparative example No.21 of EBSP method mensuration.
Fig. 4: indent mould section form synoptic diagram.
Fig. 5: the synoptic diagram of indent method.
Fig. 6: the synoptic diagram of the sample section shape behind the indent.
Fig. 7: show the photo that Vickers' hardness distributes behind the indent on the comparative example No.22 section.
Sample is at the section photo of bending machining behind the indent that Fig. 8: Fig. 7 shows.
Embodiment
Texture
As mentioned above, the Cu-Ni-Si series copper alloy is under common creating conditions, with { 111}, { 200}, { 220}, { four crystal planes of 311} are compared, and the X-ray diffraction intensity of other crystal plane is very little.In the Cu-Ni-Si series copper alloy plate that conventional manufacturing process obtains, { X-ray diffraction intensity of 420} face is also very little so that can ignore., according to described of the present invention the creating conditions in back, can obtain based on { texture of 420} planar orientation.Present inventors find that by detailed investigation { it is just good more that the 420} planar orientation reaches bendability all the more.Its principle is summarized as follows.
As everyone knows, the Cu-Ni-Si series copper alloy has face-centered cube (fcc) structure.When having the material stress following generation viscous deformation (slippage) outside of face-centerd cubic structure, its slip plane is that { 111} face, slip direction are＜110〉direction.In polycrystal, can the complexity of certain crystal grain in certain direction generation sliding deformation be described with the Heidi Schmid factor (Schmid factor).The so-called Heidi Schmid factor is that certain crystal grain is adding under the stress, acts on the shearing stress on its slip system and the ratio of applied stress.Specifically, if the angle of the direction of applied stress and slip plane normal is the angle of φ and slip direction when being λ, the value of the Heidi Schmid factor then is cos φ cos λ, and its maximum value is 0.5.The Heidi Schmid factor big more (value) near 0.5, the shearing stress that acts on the slip direction is just big more, and the distortion of this crystal grain is just easy more and work hardening is also more little.
Fig. 1 has shown the distribution of the Heidi Schmid factor on the contrary pole graph of standard of face-centered cubic crystal.＜120〉the Heidi Schmid factor 0.490 of direction, approaching maximum value is 0.5.And that the Heidi Schmid factor of other direction compares is less, such as＜100〉direction is 0.408, and＜113〉direction is 0.445, and＜110〉direction is 0.408, and＜112〉direction is 0.408,＜111〉direction is 0.272.Therefore, in crystalline＜120〉during the direction stress application, face-centered cubic crystal is easy to deform.
Here need to prove, the form of using minimum approximate number when crystalline orientation distributes (texture) is traditionally described with pole graph, and when measuring crystalline orientation and distribute with the X-ray diffraction method, owing to only be both odd number or be both the even crystal plane diffraction takes place.Therefore, on the pole graph such as 210}, and 110} etc. in the X-ray diffraction method with { 420} and { 220} waits and represents.
So that { texture of 420} planar orientation is meant, { ratio of the crystal grain that 420} (or { 210}) crystal plane is parallel with plate face (rolled surface) is than higher texture for it.When the 210} crystal plane is parallel with the plate face and the vertical direction of plate face (ND) be＜120〉direction, its Heidi Schmid factor approaches maximum value 0.5, and is therefore little in ND direction easy deformation and work hardening.When in contrast to this, the Cu-Ni-Si series copper alloy has general rolling texture (that is, based on { texture of 220} planar orientation) and the vertical direction of plate face (ND) be＜220〉(or＜110 〉) directions; When having general recrystallization texture (that is, based on { texture of 311} planar orientation) and the vertical direction of plate face (ND) be＜113〉direction.＜110〉and＜113〉direction the Heidi Schmid factor is respectively 0.4 and 0.45, less than＜120 direction 0.490.Thereby the work hardening capacity when the ND direction is out of shape is than higher.
In indent bending machining method, the work hardening capacity when going up distortion with the vertical direction of plate face (ND) is very important.Rupture when the very big (see figure 7) of work hardening capacity, bending machining after the indent easily in the position that near during indent groove thickness of slab reduces.Have among the present invention satisfy formula (1) based on { the situation of the texture of 420} planar orientation, with have general rolling texture or recrystallization texture and both intermediatenesses are compared, work hardening capacity during indent is little, therefore can cause the remarkable improvement of indent bendability.
Further, have satisfy formula (1) based on { under the situation of the texture of 420} planar orientation, crystal grain when the 210} crystal plane was parallel with the plate face, direction parallel with rolling direction LD on the plate face was＜100〉and roll the vertical direction TD of direction and also be＜120〉direction.This point obtains confirming in practice.As follows and the plate face parallel junction crystal face of concrete example is that { during 120}, the LD direction is [001], and TD also is [2,1,0].In this case, the Heidi Schmid factor of LD direction is 0.408, the Heidi Schmid factor of TD direction is 0.490.In contrast to this, when the Cu-Ni-Si series copper alloy has general rolling texture and plate face parallel junction crystal face be 110}, the LD direction is＜112, the TD direction is＜111.The Heidi Schmid factor of LD direction is 0.408, the Heidi Schmid factor of TD direction is 0.272.When having general recrystallization texture and plate face parallel junction crystal face be 113}, the LD direction is＜112, the TD direction is＜110.The Heidi Schmid factor of LD and TD direction all is 0.408.Therefore, have among the present invention satisfy formula (1) based on { the situation of the texture of 420} planar orientation, with have general rolling texture or recrystallization texture and both intermediatenesses are compared, the Heidi Schmid factor of LD and TD direction is all than higher, thereby the bendability on LD and TD direction all may improve.
Metal sheet is when flexural deformation, because the orientation difference of crystal grain, all crystal grain is not that the same distortion takes place.Crystal grain and the branch of not allowing yielding crystal grain that easy deformation is wherein arranged.At the diastrophic initial stage, viscous deformation takes place earlier in the crystal grain of easy deformation, because intercrystalline viscous deformation difference, forms small rough state at the outside surface of plate.Along with the increase of flexural deformation degree, rough degree increases, up to crackle even fracture occurring.As mentioned above, have satisfy formula (1) based on { under the situation of the texture of 420} planar orientation, ND, easy deformation all on three directions of LD and TD, therefore, like product is in the past compared, and under the situation that does not need special crystal grain thinning, indent bendability and common bendability is significantly improved.
According to present inventors' he result of investigation, have above-mentioned effect so that { texture of 420} planar orientation can limit with following formula (1).
I{420}/I
0{420}>1.0......(1)
Wherein I{420} is this copper alloy plate surface { X-ray diffraction intensity of 420} crystal plane; I
0{ 420} is the standard pure copper powder { X-ray diffraction intensity of 420} crystal plane.
Formula (1) below satisfying ', effect can be better.
I{420}/I
0{420}>1.5......(1)’
So that { texture of 420} planar orientation mainly is in following solution treatment, forms as recrystallization texture.But, in the cold rolling and final cold-rolled process in the centre of after solution treatment, carrying out, along with the increase of rolling rate, so that { rolling texture of 220} planar orientation prosperity is gradually got up in order to improve intensity.Along with { increase of 220} planar orientation density, { 420} planar orientation density can reduce thereupon.Can make formula (1) and formula (1) by adjusting rolling rate ' kept.Because so that { the too flourishing reduction that can cause processibility of the rolling texture of 220} planar orientation, following (2) formula preferably is met.In addition, consider the balance of intensity and bendability, preferably make following formula (2) ' be met.
I{220}/I
0{220}≦3.0......(2)
0.5≦I{220}/I
0{220}≦3.0......(2)’
Wherein I{220} is this copper alloy plate surface { X-ray diffraction intensity of 220} crystal plane; I
0{ 220} is the standard pure copper powder { X-ray diffraction intensity of 220} crystal plane.
Average crystal grain diameter
As previously mentioned, though average crystal grain diameter is more little favourable more to improving bendability, can cause the reduction of proof stress slackness.According to the result of present inventors' probe, if final average crystal grain diameter more than 10 μ m, preferably surpasses 10 μ m, just can satisfy, such as the requirement of automobile usefulness unitor to the exigent purposes of proof stress slackness.But,,, cause the surface irregularity at bending machining position easily, bendability is reduced because crystal grain is too thick if average crystal grain diameter surpasses 60 μ m.Therefore, average crystal grain diameter preferably below 60 μ m, more preferably is controlled between 15～40 μ m.Final average crystal grain diameter almost completely depends on the state after the solution treatment, can control average crystal grain diameter by following solution treatment condition.
Alloy composition
In this manual, be 3 yuan that Cu-Ni-Si alloy and the alloy that has added other elements such as Sn, Zn on this basis are referred to as the Cu-Ni-Si series copper alloy.
Ni (nickel) and the form of Si (silicon) by from supersaturated solid solution, separating out, intensity, electroconductibility, thermal conductivity and the proof stress slackness of raising material.If the amount of Ni is less than 0.7 weight %, perhaps the amount of Si is difficult to achieve the above object effectively less than 0.2 weight %.But,, thereby bendability and proof stress slackness are reduced if the amount surplus of Ni and Si causes the formation of thick precipitate easily.Simultaneously, also be not easy to obtain so that { 420} is oriented to main recrystallization texture, thereby is difficult to obtain having the sheet material of excellent bendability in solution treatment.Therefore, the amount of Ni must be controlled at below the 4.2 weight %, preferably below 3.5 weight %, more preferably below 3.0 weight %.The amount of Si must be controlled at below the 1.0 weight %, preferably below 0.7 weight %.The amount that special ideal composition range is Ni is most preferably between 1.2～2.5 weight %; The amount of Si is between 0.3～0.6 weight %
The precipitate of Ni and Si is mainly with Ni
2Si is main.Ni in the alloy and the Si form of establishing a capital with precipitate that also differs after ageing treatment exists, and the form with solid solution is present in the Cu matrix more or less.When Ni and Si exist with the form of solid solution, though the effect that improves intensity is also arranged, compare when form with precipitate exists, its strengthening effect is less, and is the major cause that causes the electroconductibility reduction.Therefore, the ratio of Ni and Si amount is preferably as much as possible near precipitate Ni
2The atomic ratio of Si (2:1).When the amount of element is represented with weight % in the present invention, the scope of Ni/Si is controlled between 3.0～6.0, preferably between 3.5～5.0.But, in following alloy, contain Co, Cr etc. can and Si when forming the element of precipitate, the scope of Ni/Si preferably is controlled between 3.0～4.0
The effect that Sn (tin) has solution strengthening and improves the proof stress slackness.Give full play to these effects, the amount of Sn is preferably more than 0.1 weight %.But, if the amount of Sn surpasses 1.2 weight %, can cause the rapid decline of electroconductibility.Therefore, when being necessary to add Sn, the amount of Sn must be controlled at below the 1.2 weight %.The amount of Sn preferably is controlled between 0.1～1.2 weight %, more preferably between 0.2～0.7 weight %.
Zn (zinc) has the weldability of improvement and castibility, improves the effect of intensity.If add Zn, cheap brass waste material can be used as cast raw material and uses, and has the effect that reduces cost.But,, can cause the decline of electroconductibility and anticorrosion stress-resistant if the amount of Zn surpasses 2.0 weight %.Therefore, when being necessary to add Zn, the amount of Zn is controlled at below the 2.0 weight %.It is above fully to obtain above-mentioned effect, preferably between 0.3～1.0 weight % that the amount of Zn preferably is controlled at 0.1 weight %.
Mg (magnesium) has the effect that improves the proof stress slackness and take off S (sulphur).Give full play to these effects, the amount of Mg is preferably more than 0.01 weight %.But Mg is the element of easy oxidation, if the amount of Mg surpasses 1.0 weight %, can cause the rapid decline of castibility.Therefore, when adding Mg, the amount of Mg must be controlled at below the 1.0 weight %.The amount of Mg preferably is controlled between 0.01～1.0 weight %, more preferably between 0.1～0.5 weight %.
Co (cobalt) can form precipitate with Si, and Co also can separate out as simple substance.That is to say, if contain Co in the alloy, Co can with the copper matrix in be in solid solution condition Si react forming precipitate, and remaining Co itself also can separate out.Thereby, have the effect that intensity of making and electroconductibility improve simultaneously.Give full play to such effect, the amount of Co is preferably more than 0.1 weight %.But, Co is more valuable element, and amount is crossed the increase that conference causes raw materials cost.Therefore, adding under the situation of Co, the amount of Co is being controlled at below the 2.0 weight %.The amount of Co preferably is controlled between 0.1～2.0 weight %, more preferably between 0.5～1.5 weight %.
{ 200}, { formation of recrystallize orientations such as 420}, Fe has the inhibitions { effect of 220} orientation formation owing to promote after solution treatment.Concrete, when containing the Fe of appropriate amount, { reduction of 220} orientation density is with { increase of 420} orientation density, this helps to strengthen bendability to tend to generation.In order to obtain effect of sufficient, preferably set up the above Fe content of 0.01 quality %.Yet too much Fe content tends to cause that { the too much formation of 200} orientation causes the { reduction of 420} orientation density thus.Therefore, when containing Fe, Fe content should be below the 1.0 weight %.Therefore, wish Fe content in 0.01 weight %-1.0 weight % scope, more preferably in 0.1 weight %-0.5 weight % scope.
For other element, can contain elements such as Cr, B, P, Zr, Ti, Mn and V as the case may be.Such as, Cr, B, P, Zr, Ti, Mn and V can improve intensity and proof stress slackness.Cr, Zr, Ti, Mn and V can form high melting point compound with the S, the Pb that contain in the impurity etc., and B, P, Zr, Ti have the effect of the crystal grain after the refinement casting, can improve the hot workability of alloy.During in containing elements such as Cr, B, P, Zr, Ti, Mn and V one or more, give full play to above-mentioned various effects, its total amount is preferably more than 0.01 weight %.But the amount of above-mentioned various elements is too much, causes the reduction of hot workability or cold-workability easily, and the increase of raw materials cost.Therefore, total amount of these elements preferably is controlled at below the 3 weight %, more preferably below 2 weight %, also preferably below 1 weight %, most preferably below the 0.5 weight %.
Characteristic
In order to satisfy the miniaturization of electrical and electronic parts and the needs of densification, the tensile strength that requires employed copper base alloy is more than 700MPa, preferably more than 750MPa.Simultaneously, if when parallel with rolling direction and vertical direction is called LD and TD direction on the plate face, require the bending machining sexual satisfaction of LD and TD direction, the ratio R/t that the minimum bending radius R of crackle and thickness of slab t do not take place during 90 ° of W type bending machining is more preferably less than 0.5 preferably less than 1.0.In addition, for the shape and size precision of the parts after the further raising bending machining, wish that the bendability R/t of LD direction behind indent is 0.The evaluation method of the bendability behind the indent is shown in following example.The bendability of LD direction described here is meant that by the parallel sample that cuts with rolling direction of the length direction of sample, the axis of bending during bending machining is the TD direction.Equally, the bendability of TD direction is meant that by the vertical sample that cuts with rolling direction of length direction of sample, the axis of bending during bending machining is the LD direction.
The proof stress slackness on the purposes of automobile unitor with material etc., the value particularly important of TD direction.Therefore, be that the stress relaxation rate of the sample of TD is estimated to the length direction of sheet material.Sample is that when keeping 1000 hours down for 150 ℃, stress relaxation rate is preferably below 5%, more preferably below 3% under 80% the state of 0.2% yielding stress of sample at maximum surface stress.
Manufacture method
Above-described copper alloy plate of the present invention for example can be made by following general technology flow process.That is,
Fusion/casting-hot rolling-cold rolling-solution treatment-centre is cold rolling-ageing treatment-finally cold rolling-low-temperature annealing
But, as described below like that, several control of process condition wherein are very important.In addition,, according to actual needs, after hot rolling, can optionally wash one's face (facing), can carry out optional pickling after the thermal treatment, grind or degreasing etc. though toply do not mention.Further specify with regard to each technology below.
[fusion casting]
Use the continuous casting of general copper alloy and D.C.casting method etc. just passable.
[hot rolling]
For the generation that prevents to separate out in course of hot rolling, the hot rolling of Cu-Ni-Si series copper alloy generally all is to carry out more than 700 ℃ even more than 750 ℃, and wants chilling after the hot rolling end of a period.But, be the copper alloy plate that is difficult to obtain to have special texture described in the invention according to the hot-rolling method of such common-sense.Present inventors are by a large amount of and detailed research, and wherein they change processing condition by the hot rolling of above-mentioned condition on a large scale, but do not find can produce so that { 420} is oriented to the necessary hot-rolling method of main texture.Therefore present inventors study in more detail.The result is, in 950 ℃～700 ℃ temperature range, be rolled earlier, the rate that in being lower than 700 ℃～400 ℃ temperature range, is rolled then surpass 40% rolling.
When being rolled, recrystallize taking place easily, eliminates cast structure and make composition and grain structure uniform distribution in the temperature range more than 700 ℃.But, if rolling temperature surpasses 950 ℃, the individual bits of ingot casting is equipped with and may produces cracking in the operation of rolling.This mainly is because the skewness of the alloying element in the cast structure has caused the melting point reason on the low side in indivedual places.Therefore, rolling temperature had better not be above 950 ℃.In order further to promote the uniform distribution of composition and grain structure, the rate that is rolled in 950 ℃～700 ℃ temperature range rolling more than 60% is very effective.This can make texture more even.But 60% the rolling rate of obtaining in single passage needs big rolling load, by be divided into multi-pass rolling produce amount to maximum 60% or higher rolling rate be acceptable.In addition, it is also important that the rate that in being lower than 700 ℃～400 ℃ temperature range, is rolled rolling more than 40% in the present invention.Like this, under the situation that has a small amount of precipitate to produce, be rolled, can promote the formation of rolling texture, and then promote in the combination of cold rolling and solution treatment described later so that { 420} is oriented to the formation of main recrystallization texture.At this moment, also can carry out a plurality of rolling passes being lower than 700 ℃ to 400 ℃.More effective is to carry out the hot rolled final pass under the temperature below 600 ℃.The total rolling rate of above-mentioned hot rolled should be roughly 80～95%.
Here, the rolling rate ε of each temperature range is calculated by formula (3).
ε(％)＝(t
0-t
1)/t
0×100......(3)
For example suppose, thickness of slab is that the 120mm continuously cast bloom carries out first rolling pass 950～700 ℃ of temperature ranges, rollingly carry out (it is acceptable that continuously cast bloom is returned reheating furnace) in the temperature range more than 700 ℃, thickness of slab after temperature range is finished final rolling pass more than 700 ℃ is 30mm, and to proceed rolling and carry out final hot rolling pass in the temperature range that is lower than 700 ℃ to 400 ℃ be the hot-rolled sheet of 10mm to obtain final thickness.In this case, according to formula (3), the rolling rate in 950 ℃～700 ℃ the temperature range is, (120-30)/and 120 * 100%=75 (%); The rolling rate that is lower than 700 ℃ to 400 ℃ temperature range is, (30-10)/and 30 * 100=66.7 (%).
[cold rolling]
Next the rate that is rolled is more than 85%, is preferably cold rolling more than 90%.The high rolling rate in this stage cold rolling to after in the solution treatment so that { it is extremely important that 420} is oriented to the formation of main recrystallization texture.The recrystallization texture height depends on the cold rolling rate before the recrystallize.Specifically, when rolling rate 60% when following, so that { crystalline orientation of 420} face does not have substantially, and along with the increase of the rolling rate in this stage, rolling rate begins to increase gradually in 60%～80% interval, and rolling rate sharply increased greater than 80% o'clock.Therefore, in order to obtain so that { 420} is oriented to main recrystallization texture, and cold rolling rolling rate is necessary to be preferably in more than 90% more than 85%.The upper limit of cold rolling rate need not concrete qualification, because the rolling rate of obtainable maximum is limited by milling train power etc.But obtained the result easily in about rolling rate below 98%, because this has been avoided crack at edge etc.
In addition, in the manufacture method among the present invention, promptly after hot rolling and in the cold rolling pass before the solution treatment, do not insert process annealing.If not, will cause after the solution treatment { the 420} orientation significantly reduces.
[solution treatment]
Solution treatment generally makes the solute element solid solution and makes the material recrystallize.It is to make so that { 420} is oriented to main recrystallization texture and forms that the present invention also has a prior purpose on this basis.Solid solution temperature is preferably between 700～850 ℃.Temperature is low excessively to cause the not enough and recrystallize fully of the solid solution capacity of solute element.Otherwise temperature is too high will to cause the too thick of crystal grain.Both of these case finally all can not get the good high-strength panel of bendability down.In addition, be rapidly heated 700 ℃ to so that { it is also very effective that 420} is oriented to the formation of main recrystallization texture.Heat-up rate is too slow, can cause the generation that recovers and separate out in the way of heating up, to so that { it is unfavorable that 420} is oriented to the formation of main recrystallization texture.Therefore, specifically, wish that heating-up time from 100 ℃ to 700 ℃ temperature range is preferably below 20 seconds, most preferably below 15 seconds.
Treatment time during above-mentioned 700～850 ℃ of solution treatment and the final temperature that arrives should be between 10～60 μ m by the average crystal grain diameter of recrystal grain (twin boundary is not as crystal boundary), preferably set between 15～40 μ m.Average crystal grain diameter is too tiny, can cause the reduction of proof stress slackness, and is unfavorable for so that { 420} is oriented to the formation of main recrystallization texture.Otherwise average crystal grain diameter is excessive, causes the surface irregularity at bending machining position easily, and bendability is reduced.The recrystal grain diameter changes according to cold rolling rate and the chemical constitution before the solution treatment.Suitable solid solution temperature and time change to some extent with alloying constituent.Can pass through preliminary experiment, find out the relation of temperature-time-average crystal grain diameter and grasp.Specifically, the suitable solution treatment condition of the copper alloy in the composition range given to this invention is in the time range of 700～850 ℃ temperature ranges and 10 seconds～10 minutes.
[middle cold rolling]
The rate that then can be rolled cold rolling below 50%.The formation of precipitate in the ageing treatment after cold rolling can the promotion in this stage shortens to the expection needed ageing treatment time of characteristic (electroconductibility, hardness) that reaches.Though cold rolling can the causing in this stage, { increase of 220} orientation if rolling rate is controlled at below 50%, still can keep enough { 420} orientations.Therefore, this stage, cold rolling rolling rate was necessary to be controlled at below 50%, preferably in 0～35% scope.If cold rolling rolling rate of this stage is excessive, the orientation relationship of (1) formula that not only can be not being met, and inhomogeneous generation of separating out with overaging in the ageing treatment after causing easily.Rolling rate is to represent not carry out the cold rolling of this stage in 0% o'clock, and the ageing treatment that directly enters next stage.Among the present invention,, also can omit the cold rolling of this stage in order to enhance productivity.
[ageing treatment]
Next carry out ageing treatment.Ageing treatment is carried out helping improving under the condition of alloy specific conductivity and intensity, and does not significantly improve the carrying out of temperature.Aging temperature is too high, make easily obtain after the solution treatment { the 420} orientation dies down, thereby can not get excellent in vending workability.Specifically, wish that aging temperature is preferably between 400～500 ℃, more preferably between 420～480 ℃.The ageing treatment time roughly just can obtain good result at 1～10 hour in the scope.
[finally cold rolling]
In order further to improve the intensity of material, can after ageing treatment, carry out finally cold rolling.But, { the 220} orientation can increase along with the increase of rolling rate.Therefore, if rolling rate is excessive, { rolling texture of 220} orientation has comparative advantage, just can not get improving simultaneously intensity and the necessary orientation of bendability.Present inventors if find that rolling rate is controlled at below 50%, just can be met the orientation relationship of formula (1) by detailed research.In addition, with middle cold rolling the same, finally cold rolling neither requisite technological process.
The final thickness of slab of copper alloy of the present invention can be preferably between 0.08～0.5mm between 0.05～1.0mm.
[low-temperature annealing]
Final cold rolling after, can reduce the room and the dislocation at slip plane place by low-temperature annealing, improve the proof stress slackness.Simultaneously can reduce and eliminate the residual stress in the sheet material, raising bendability and significantly do not reduce intensity.Electroconductibility is increased.Heating temperature in the low-temperature annealing preferably sets in 150～550 ℃.If temperature is set De Taigao, cause the softening of sheet material easily.Otherwise,, do not reach expected effect if temperature is set too lowly.Hold-time is preferably more than 5 seconds, just can reach good effect with interior low-temperature annealing in common 1 hour.In addition, do not carrying out to omit low-temperature annealing under the final cold rolling situation.
Embodiment
Utilize vertical fusion casting machine to cast composition ingot casting as shown in table 1.Except some comparative examples, downcutting thickness from ingot casting is the sample (thickness is 180mm) of 50mm.Carry out hot rolling after these samples are heated to 950 ℃.Except a part of comparative example, rolling procedure is more than 60% by the rolling rate of 950 ℃～700 ℃ temperature range, and is lower than and also is rolled in 700 ℃ the temperature range and sets.Except a part of comparative example, the final passage of hot rolled is between setting 600 ℃～400 ℃.The rolling rate that ends from the ingot casting to the hot rolling is roughly about 90%.Remove the oxide film on surface after the hot rolling by mechanical polishing (washing one's face).Then carry out carrying out solution treatment after cold rolling with various rolling rates.Thermopair is enclosed on surface at sample during solution treatment, the METHOD FOR CONTINUOUS DETERMINATION variation of temperature, and obtain 100 ℃ to 700 ℃ heating-up time.Except a part of comparative example, according to alloying constituent in the time range of 700～850 ℃ temperature range and 10 seconds～10 minutes, by adjusting temperature and time, making the average crystal grain diameter (twin boundary not being regarded as crystal boundary) after the solution treatment is 10～60 μ m.Then, remove in certain embodiments, it is cold rolling that the sheet material after the solution treatment carries out the centre with one in the multiple rolling rate, subsequently ageing treatment.Ageing treatment makes its hardness reach maximum value by adjusting aging time under 450 ℃ of temperature.Best solution treatment condition and ageing treatment time for alloy composition are learnt by prior experiment.Sample after the part ageing treatment carries out the finally cold rolling of different rolling rates, and 5 minutes low-temperature annealing is carried out in cold rolling back in 400 ℃ process furnace.Sample is obtained by aforesaid way.At last the sample that obtains is carried out evaluating characteristics.The thickness of slab of sample is 0.2mm.Mainly creating conditions of each sample is as shown in table 2.
Part comparative example (No.21,22,24,25) utilizes common operation, such as, in hot rolling and the solution treatment intermediary cold-rolled process, roll about process annealing of carrying out 550 ℃ * 3hr at 50% o'clock at thickness of slab.
In addition, also the Cu-Ni-Si series copper alloy C7025 (thickness of slab is 0.2mm) that circulates is on the market carried out evaluating characteristics (No.34).
[table 1]
Annotate: the expression of rolling off the production line has exceeded the scope of the present invention's regulation
The sample character that obtains has been carried out following every evaluation.That is: crystal grain texture, X-ray diffraction intensity, electric conductivity, tensile strength, stress relaxation rate, common bendability, the bendability behind the indent.And the distribution of orientations of part sample measured with Electron Back-Scattered Diffraction pattern (EBSP) method.
[crystal grain texture]
The surface of sample (rolling surface) is observed under opticmicroscope through after polishing and corroding.Average crystal grain diameter is to measure by the division lines method among the JIS H0501.
[X-ray diffraction intensity]
The surface of sample (rolling surface) is measured { 420} face and { the X-ray diffraction integrated intensity of 220} face with X-ray diffraction device (XRD) to said sample and standard fine copper powdered sample through with after the polishing of #1500 waterproof abrasive paper.Then, calculate I{420}/I in (1) formula and (2) formula according to the X-ray diffraction integrated intensity of measuring
0{ 420} and I{220}/I
0{ 220}.Condition determination is fluorescent tube: Mo-K α; Tube voltage: 20kV; Tube current: 2mA.
[electric conductivity]
Electric conductivity is measured according to the method for JIS H0505 regulation.
[tensile strength]
Cut out LD tensile test piece (No. 5 samples of JIS) down from each material.Tensile strength is measured according to the method for JIS Z2241 regulation.Mean value with 3 times measurement results is as the criterion.
[stress relaxation rate]
Cut out down from each material that length direction is the bend specimen (width is 10mm) of TD, make sample become arc with anchor clamps, and by the length that following formula is adjusted anchor clamps make the surface stress of specimen length direction middle position be sample 0.2% yielding stress 80%.
Surface stress (MPa)=6Et δ/L
0 2
Wherein:
E: coefficient of elasticity (MPa)
T: the thickness of sample (mm)
δ: the height of sample arc of curvature (mm)
L
0: the length of anchor clamps (mm), the horizontal throw of the sample go-and-retum that promptly is fixed in the test process
With anchor clamps and sample fixing after, kept 1000 hours at 150 ℃.Then, remove anchor clamps and press the computed stress relaxation rate.
Stress relaxation rate (%)=(L
1-L
2)/(L
1-L
0) * 100
Wherein:
L
1: the specimen length (mm) when measuring beginning
L
2: the horizontal throw (mm) at sample two ends, experiment back
The material of stress relaxation rate below 5% is considered to can be used as the exigent automobile unitor of proof stress slackness used with material.
[conventional bendability]
Length direction is respectively LD bend specimen and the TD bend specimen (width is 10mm) of LD and TD, carries out bending machining by 90 ° of W type bending machining methods of JIS H3110 regulation.Specimen surface after the bending machining and section are observed under 100 times with opticmicroscope.The minimum bending radius R of crackle is not taken place.With the value of the ratio R/t of minimum bending radius R and thickness of slab t as evaluation to bendability.Sample to the same terms carries out 3 times same tests, the result of evaluation with the value of R/t the poorest in 3 times as evaluation result.The value of the LD of sample and the R/t of TD is all below 0.5, and then the bendability of this sample is qualified.
[the bending machining method behind the indent]
Length direction is the narrow rectangular specimen (width is 10mm) of LD, with the bench-type that shows among Fig. 4 (width of bench-type bossing is 0.1mm, and the inclination angle of two sides is 45 °) indent mould, with pressure indent on the whole width of sample of 10kN.The length direction of groove (direction that promptly is parallel to groove) is vertical with the length direction of sample.As shown in Figure 6 like that, the measured value of the degree of depth of the groove that obtains (highly) δ is 1/4～1/6 of thickness of slab t.
To the sample of trough of belt, carry out bending machining by 90 ° of W type bending machining methods of JIS H3110 regulation.At this moment, allow the facing down of sample trough of belt, bending machining is carried out with above-mentioned common bending machining in the position of the most advanced and sophisticated R=0mm of the central protrusion of corresponding and 90 ° of W type bending moulds the samely.
Specimen surface after the bending machining and section are observed under 100 times with opticmicroscope.Representing with G (good) of crackle do not take place, representing with P (poor) of crackle takes place, what take place to rupture represents with R (breaking).Sample to the same terms carries out 3 times same tests, and as evaluation, G is qualified with result the poorest in 3 times.
[EBSP mensuration]
EBSP is the abbreviation of Electron Back-Scattering Diffraction Pattern, is by the Kikuchi lines analysis to certain any diffraction spot of specimen surface, determines the method for this crystalline orientation.Produce distortion for fear of specimen surface, adopt vibrations polishing method (a kind of not applying pressure, but the method for polishing sample by the vibrations of sample bench) surface of polishing sample, then, utilize EBSP to measure crystalline orientation and distribute, and therefrom obtain its { area percentage that crystal grain occupied that the 120} crystal plane is parallel with plate surface (rolling surface).Here by regular practice, with＜120〉direction is the center, 10 ° of scopes of deviation with the area percentage of interior crystal orientation as { the area percentage of 120} crystal plane, this value is preferably more than 20%, more preferably more than 25%.
The result of evaluating characteristics is as shown in table 2." the common bendability " of table 2, the length direction that LD in the bending machining method behind the indent and " stress relaxation rate " project and TD represent sample.
[table 2]
From table 2, can see, all examples all have the grain orientation relation that satisfies formula (1), electric conductivity more than 35% IACS in, have the high strength of tensile strength more than 700MPa, the R/t with LD and TD direction is less than the bendability of 0.5 excellence.Further, be in 0 the bendability crackle not to take place at LD direction R/t behind indent, this is useful especially.In addition, the proof stress slackness that has the excellence of stress relaxation rate below 5% of TD direction important on the purposes of automobile unitor with material etc.In addition, the mensuration of EBSP method the percentages show of 120} orientation the present invention have high { 420} area density.
In contrast to this, the alloy that comparative example No.21～25th and example No.1～4 have identical component, the sheet material of making according to common manufacture method (such as, the hot-rolled temperature of final passage more than 650 ℃ or 700 ℃, and between hot rolling and solution treatment, having inserted process annealing etc.).These common features are that { 420} face X-ray diffraction intensity is low, exists opposite each other relation between intensity and the bendability and between bendability and the proof stress slackness.Particularly, the indent bendability is all very low.
Comparative example No.26 and No.27 are because the amount of Ni and Si has exceeded the scope of the present invention's regulation, and do not obtain the example of superperformance.The Ni of No.26 and the amount of Si are too low, the result since the precipitate that generates very little, even intensity is low and added Mg and also do not obtain good proof stress slackness.Simultaneously, because the precipitate that generates in the hot rolling stage very little, even cold rolling rolling rate does not afterwards obtain so that { the 420} face is its crystalline orientation that mainly is orientated up to more than 90% yet.Do not obtain good indent bendability although result's intensity is high yet.The Ni of No.27 and the amount of Si are too high, do not have suitable solution treatment condition.Crystal grain is too tiny as a result, and { the 420} area density is very low.Though intensity is very high, bendability and proof stress slackness are very low.
Comparative example No.28～31st because the solution treatment condition has exceeded regulation of the present invention, and do not obtain the example of superperformance.The solid solution temperature of comparative example No.28 too high (870 ℃) has caused the too thick of crystal grain and has not obtained excellent in vending workability.On the contrary, the solid solution temperature of No.29 low excessively (650 ℃), recrystallize take place fully, have caused mixed kernel structure, intensity as a result, and bendability and proof stress slackness worsen comprehensively.No.30 temperature rise rate in the solution treatment process is slow, causes occur recovering, and has discharged some distortion/strains, the result be with 420} as the crystalline orientation of main orientation a little less than and bendability poor.No.31 is in order to improve bendability, and by adjusting solid solution temperature, making average crystal grain diameter is 3 μ m.So, though improved bendability, because the too tiny reduction that causes the proof stress slackness of crystal grain.
Comparative example No.32～33rd, intermediate rolling or final rolling rolling rate have surpassed set upper limit of the present invention, and do not obtain the example of superperformance.No.32 is that final rolling rolling rate is too high, though have very high intensity, the example that bendability but significantly worsens.Though it is too high that the final rolling rolling rate of No.33 does not have, because the rolling rate of intermediate rolling is too high, cause the reduction of 420} area density, thus good characteristic do not obtained.
Comparative example No.34 is the C7025 alloy that is considered to have excellent in vending workability and proof stress slackness in the existing goods.But, compare with the routine No.5 of the present invention of sample ingredient with having basically, all inferior on bendability and proof stress slackness.
Fig. 2 and Fig. 3 are respectively with the example No.1 of EBSP method mensuration and the contrary pole graph of comparative example No.21.The zone that the figure dotted line impales is so that { the 120} face is the center, and 10 ° of scopes of deviation are with interior zone.Can see, example (Fig. 2) { the 120} area density is higher than comparative example (Fig. 3) significantly, example thereby the higher Heidi Schmid factor (with reference to figure 1) is arranged.This is the major cause of the present invention's bendability (particularly indent bendability) that can improve sheet material significantly.
Fig. 7 is the section photo of sample behind indent of comparative example No.22, and numeral wherein is the value of Vickers' hardness.Can see that tangible work hardening has taken place the part of thickness of slab attenuation near groove.Fig. 8 be behind the indent that shows among Fig. 7 sample at the section photo of bending machining.Therefrom can see the appearance that crackle takes place.
Claims (10)
1. copper alloy plate, it contains the Ni of 0.7～4.2 weight %, the Si of 0.2～1.0 weight %, all the other are essentially Cu, and this copper alloy plate have satisfy below the grain orientation of formula (1),
I{420}/I
0{420}>1.0 ......(1)
Wherein I{420} is this copper alloy plate surface { X-ray diffraction intensity of 420} crystal plane; I
0{ 420} is the standard pure copper powder { X-ray diffraction intensity of 420} crystal plane.
2. the copper alloy plate of claim 1, its also have satisfy below the grain orientation of formula (2),
I{220}/I
0{220}≦3.0 ......(2)
Wherein I{220} is this copper alloy plate surface { X-ray diffraction intensity of 220} crystal plane; I
0{ 220} is the standard pure copper powder { X-ray diffraction intensity of 220} crystal plane.
3. the copper alloy plate of claim 1 or claim 2, its average crystal grain diameter that has is 10～60 μ m.
4. each copper alloy plate in the claim 1～3, it further contains the following Sn of 1.2 weight %, the Zn that 2.0 weight % are following, the Mg that 1.0 weight % are following, one or more among the following Fe of Co that 2.0 weight % are following and 1.0 weight %.
5. each copper alloy plate in the claim 1～4, it further contains and is selected from Cr, B, P, Zr, Ti, one or more among Mn and the V, and also its total amount is below the 3 weight %.
6. the manufacture method of each copper alloy plate in the claim 1～5, it comprises that order carries out following steps: hot rolling, the rolling rate in 950～400 ℃ the temperature range is cold rolling, 700～850 ℃ the interior solution treatment of temperature range 85% or more, rolling rate is that 0～50% centre is cold rolling, the ageing treatment in 400～500 ℃ the temperature range and rolling rate be 0～50% finally cold rolling
Wherein, in the hot-rolled step of this method, in 950 ℃～700 ℃ temperature range, carry out initial passage, and the rate that in being lower than 700 ℃～400 ℃ temperature range, is rolled rolling more than 40%.
7. the manufacture method of the copper alloy plate of claim 6, wherein in the hot-rolled step of this method, rolling more than 40% of the rate that in 950 ℃～700 ℃ temperature range, is rolled rolling more than 60%, the rate that in being lower than 700 ℃～400 ℃ temperature range, is rolled.
8. the manufacture method of claim 6 or 7 copper alloy plate, wherein in the solution treatment step, from 100 ℃ to 700 ℃ heating-up times below 20 seconds.
9. the manufacture method of each copper alloy plate in the claim 6～8, wherein, in the solution treatment step, temperature by adjusting soaking time and finally reaching in 700～850 ℃ temperature range, make that the average crystal grain diameter of recrystal grain is between 10～60 μ m after the solution treatment, and carry out this processing.
10. the manufacture method of each copper alloy plate in the claim 6～9 is characterized in that, carry out final when cold rolling, in final low-temperature annealing of carrying out 150～550 ℃ after cold rolling.
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| JP2007032623 | 2007-02-13 | ||
| JP2007-032623 | 2007-02-13 | ||
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| JP2007326559 | 2007-12-18 | ||
| JP2007326559A JP4189435B2 (en) | 2007-02-13 | 2007-12-18 | Cu-Ni-Si-based copper alloy sheet and method for producing the same |
| JP2007-326559 | 2007-12-18 |
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| CN2008100048467A Active CN101503770B (en) | 2007-02-13 | 2008-02-04 | Cu-Ni-Si-based copper alloy sheet material and method of manufacturing same |
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| US (1) | US20080190523A1 (en) |
| EP (1) | EP1964937A1 (en) |
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| CN101871059A (en) * | 2009-04-27 | 2010-10-27 | 同和金属技术有限公司 | Copper alloy sheet and method for producing same |
| CN102985572A (en) * | 2010-07-07 | 2013-03-20 | 三菱伸铜株式会社 | Cu-Ni-Si copper alloy plate with excellent deep-draw characteristics and production method thereof |
| TWI454585B (en) * | 2013-01-25 | 2014-10-01 | Mitsubishi Shindo Kk | Copper alloys plate that is materials of terminal and connector and method of producing the same |
| CN106282654A (en) * | 2015-05-26 | 2017-01-04 | 宁波金田铜业(集团)股份有限公司 | A kind of high resiliency low cost Sn-P-Cu alloy band and preparation method thereof |
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| JP3520034B2 (en) * | 2000-07-25 | 2004-04-19 | 古河電気工業株式会社 | Copper alloy materials for electronic and electrical equipment parts |
| JP3520046B2 (en) * | 2000-12-15 | 2004-04-19 | 古河電気工業株式会社 | High strength copper alloy |
| CN1327016C (en) * | 2002-05-14 | 2007-07-18 | 同和矿业株式会社 | Copper base alloy with improved punchin and impacting performance and its preparing method |
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| JP4660735B2 (en) * | 2004-07-01 | 2011-03-30 | Ｄｏｗａメタルテック株式会社 | Method for producing copper-based alloy sheet |
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2007
- 2007-07-13 US US11/826,223 patent/US20080190523A1/en not_active Abandoned
- 2007-07-16 EP EP07013889A patent/EP1964937A1/en not_active Withdrawn
- 2007-07-17 CN CNA2007101368010A patent/CN101245422A/en active Pending
- 2007-12-18 JP JP2007326559A patent/JP4189435B2/en active Active
-
2008
- 2008-02-04 CN CN2008100048467A patent/CN101503770B/en active Active
- 2008-02-13 DE DE602008001515T patent/DE602008001515D1/en active Active
- 2008-02-13 AT AT08002634T patent/ATE471391T1/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| EP1964937A1 (en) | 2008-09-03 |
| CN101245422A (en) | 2008-08-20 |
| JP2008223136A (en) | 2008-09-25 |
| CN101503770B (en) | 2011-03-02 |
| DE602008001515D1 (en) | 2010-07-29 |
| ATE471391T1 (en) | 2010-07-15 |
| JP4189435B2 (en) | 2008-12-03 |
| US20080190523A1 (en) | 2008-08-14 |
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